Methods of using crystalline fructose

ABSTRACT

Methods of using fructose as a sweetener, particularly crystalline fructose, are disclosed. Also disclosed are methods of using dry foodstuff mixes containing fructose in a crystalline form to prepare foods for consumption while hot or cold. Further, the use of fructose and acidulants to obtain a foodstuff of desired sweetness is also disclosed. The consistent sweetness of fructose over temperature, regardless of the distribution of anomeric forms thereof, and the varying effect different acidulants have on the sweetness of fructose are also disclosed.

FIELD OF INVENTION

In one aspect, this invention relates to a method of using dry foodstuffmixes containing fructose in a crystalline form to prepare foods forconsumption while hot or cold. In another aspect, this invention relatesto the use of fructose and acidulants to obtain a foodstuff of desiredsweetness.

BACKGROUND OF THE INVENTION

L. Hyvonen, et al., "Effects of Temperature and Concentration on theRelative Sweetness of Fructose, Glucose and Xylitol", Lebensm-Wiss.u.-Technol., 10:316-320 (1977), reported that temperature has anoticeable effect on the relative sweetness of fructose, i.e., that therelative sweetness of fructose varies inversely with temperature overthe range of 5° C. to 50° C. in other words, Hyvonen reported thatfructose is sweeter, by relative sweetness, at 5° C. than at 50° C.Because the concentration of the β-D-fructopyranose anomer in a solutionalso varies inversely with temperature, it has been generally inferredby those in the art that β-D-fructopyranose is the sweetest anomer offructose in solution and that a fructose solution thus becomes sweeteras one decreases the temperature thereof. See J. Dziezak, "CrystallineFructose: A Breakthrough in Corn Sweetener Process Technology", FoodTechnology, Vol. 41, pp. 66, 67 and 72 (January 1987).

Dziezak also discloses that the sweetness of a fructose solutionincreases as the pH is decreased. However, Hyvonen, et al., "TheRelative Sweetness of Fructose, Glucose, and Xylitol in Acid Solutionsat Different Temperatures", Lebensm.-Wiss. u.-Technol. 11:11-14 (1978)reports that the relative sweetness of fructose was reduced by acids atroom temperature and, at page 14, Table 3, that citric, malic, andphosphoric each reduced the relative sweetness at room temperature toapproximately the same degree at approximately the same pH.

SUMMARY OF THE INVENTION

The various aspects of this invention can generally be divided into twobroad categories, i.e., those aspects relating to temperature phenomenaand those aspects relating to acidulant phenomena.

I. Temperature

In one aspect, this invention relates to a method of preparing afoodstuff for consumption comprising:

(a) mixing a dry foodstuff mix, said foodstuff mix comprising aparticulate solid consisting of crystalline fructose, with an edibleliquid to form a mixture;

(b) cooling a member selected from the group consisting of said mixtureand one or more components thereof, to reduce the temperature of saidmixture to a first temperature within a range of desired maximum servingtemperatures for said mixture;

(c) providing for the temperature of said mixture to rise to a secondtemperature within said range of desired maximum serving temperatures;and

(d) serving said mixture for consumption as a foodstuff at said secondtemperature.

By "dry foodstuff mix" is meant an edible mixture of components in thesolid phase (e.g., granular, powder, or the like), such mixture beingsufficiently dry to be flowable. By "providing for" is meant either ofboth passively allowing ambient conditions to raise the temperature andactively heating the mixture.

It has been found that while the relative sweetness of fructose variesinversely with temperature, the absolute sweetness of fructose, i.e.,the sweetness of fructose compared to a fructose control (as opposed toa sucrose control), does not significantly vary with temperature overthe range of 5° C. to 50° C.. Thus, a foodstuff can be formulated withfructose to have consistent absolute sweetness over a range oftemperature, typically about 5° C. to about 50° C..

Because fructose has a substantially constant absolute sweetness over arange of serving temperatures, e.g., about 5° C. to about 50° C., thefoodstuff will be as sweet at the second temperature as the firsttemperature. Thus, each individual serving should be perceived by theconsumer to be as sweet as the other, although a given serving may beserved at a warmer temperature than another serving. Such an advantagemay be most useful in the context of a beverage dispenser wherein thereis difficulty in maintaining a constant serving temperature from oneserving to the next, e.g., a commonly available "ice chest" type ofportable, insulated cooler subjected to climatic extremes.

In another aspect, this invention relates to a method of alternativelypreparing hot and cold foodstuffs for consumption comprising:

(a) mixing a first portion of a bulk reserve of a dry foodstuff mix,said dry foodstuff mix comprising a particulate solid consisting ofcrystalline fructose, with an edible liquid to form a first mixture;

(b) heating a member selected from the group consisting of said firstmixture and one or more components thereof, to elevate the temperatureof said first mixture to a temperature suitable for serving said firstmixture for consumption;

(c) mixing a second portion of said bulk reserve of said dry foodstuffmix with an edible liquid to form a second mixture; and

(d) cooling a member selected from the group consisting of said secondmixture and one or more components thereof, to reduce the temperature ofsaid mixture to a temperature suitable for serving said first mixturefor consumption.

In one set of embodiments of this aspect, the dry foodstuff mix is a dryinstant beverage mix comprised of a blend of crystalline fructose and adry flavoring material (e.g., cocoa, instant tea, instant coffee, fruitpowder, etc.), which blend can be added to a hot or cold liquid (e.g.,milk, water, etc.) to form a hot or cold beverage (e.g., cold chocolatemilk or hot cocoa, hot tea or iced tea, hot coffee or iced coffee, hotor cold fruit punch, etc.).

II. Acidulant

In another aspect, this invention relates to a method of formulating asweetened and acidulated foodstuff comprising:

(a) replacing at least a portion of the sweetener in a given sweetenedfoodstuff formulation with a particulate solid consisting of crystallinefructose, said foodstuff having a pH of below about 5 when consumed; and

(b) employing a plurality of acidulants to adjust the sweetness of saidformulation, said plurality comprising citric acid, or a salt thereof,and an edible, non-citric, fructo-sweetness active acid, or a saltthereof.

By "edible, non-citric, fructo-sweetness active acid", is meant an acidother than citric acid which is edible and which effects (i.e., eitherenhances or suppresses) the sweetness of fructose in solution at a pH ofabout 3. Examples of such acids include malic acid and phosphoric acid,both of which suppress the sweetness of fructose, i.e., they arefructo-sweetness suppressive.

It has been found that various acids have a varying effect on theabsolute sweetness of fructose in a given food formulation having a pHof less than about 5, e.g., typically about 3. In particular, it hasbeen found that citric acid has a greater suppressive effect than atleast two other acids commonly, employed as acidulants, i.e., malic acidand phosphoric acid. Accordingly, one can adjust the sweetness of a foodformulation containing fructose as a total or partial replacement foranother sweetener, by varying the relative amounts of a plurality ofacidulants. It should be made clear that this adjustment can be made toeither enhance or suppress the sweetness of the food. For example, aportion of the citric acid in a beverage can be substituted withphosphoric acid to enhance the sweetness thereof and thus allow one toreduce the amount of fructose in the beverage (and thus the caloriccontent). Alternatively, if comparatively greater fructose sugar solidsare desired in a formulation, (e.g., a pie filling), a portion of themalic acid that one might use as an acidulant can be substituted withcitric acid to reduce the sweetness without reducing the amount offructose.

In a particular aspect, this invention relates to a beverage concentratecomprising:

(a) a particulate solid consisting of crystalline fructose, saidfructose being present in a first amount; and

(b) an acidulant comprised of citric acid in a second amount, and anedible, non-citric, fructo-sweetness active acid in a third amount;

(i) said second and third amounts are, in the aggregate, sufficient toprovide a beverage having a pH of less than about 5;

(ii) said first amount is sufficient, in relation to said second andthird amounts, to provide a sweetened beverage.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of the distribution of the various anomers of fructose(as weight percent of total fructose) in solution over a range oftemperature.

FIG. 2 is a graph of the amount of β-D-fructopyranose anomer (as weightpercent of total fructose) in solution over a range of pH at threedifferent temperatures.

FIG. 3 is a graph of the amount of β-D-fructopyranose anomer (as weightpercent of total fructose) in solution over a range of total fructoseconcentration (by dry solids).

FIG. 4 is a graph of both the "relative sweetness" of fructose and the"absolute sweetness" of fructose in solution over a range oftemperature. (Table B, below, sets forth the data used to generate FIG.4.)

FIG. 5 is a graph of the absolute sweetness of fructose at differing pHby virtue of three different acids. (Table C, below, sets forth the dataused to generate FIG. 5.)

FIG. 6 is a graph superimposing both the curves of FIG. 4 and theβ-D-fructopyranose curve of FIG. 1 for purposes of comparison.

FIG. 7 is a graph superimposing both the curves of FIG. 5 and the 25° C.curve of FIG. 2 for purposes of comparison.

DETAILED DESCRIPTION OF THE INVENTION

One common element of the various aspects of this invention is fructose.The crystallization of fructose is disclosed in U.S. Pat. No. 3,883,365(Forsberg, et al.) U.S. Pat. No. 3,928,062 (Yamauchi), U.S. Pat. No.4,199,374 (Dwivedi, et al.), and U.S. Pat. No. 4,643,773 (Day). By"crystalline fructose", it is meant a solid composition whereinsubstantially all of the fructose is contained in a crystal matrix.Crystalline fructose is to be distinguished from materials containingsignificant amounts of amorphous fructose, dextrose or corn syrupby-products, e.g., dried high fructose (e.g., 42% or 55% dry solids)corn syrups and the semi-crystalline fructose disclosed in U.S. Pat. No.4,517,021 (Schollmeier). Crystalline fructose is available commericallyat a purity in excess of 99.0% as the anhydrous crystalline form ofβ-D-fructose, for example, KRYSTAR™ brand crystalline fructose availablefrom A. E. Staley Manufacturing Division of Staley Continental, Inc.,Decatur, Ill. A "particulate solid consisting of crystalline fructose"is generally granular or powder-type in nature, i.e., the weight averageparticle size generally varies from about 1 to about 1,000 microns, moretypically 250-500 microns (e.g., 300 or 450 microns).

It is known that only the β-D-fructopyranose form of fructose occurs inthe crystalline state. However, when fructose is dissolved in water,three anomeric forms are readily apparent:

1. β-D-fructopyranose (β-D-fruP)

2. β-D-fructofuranose (β-D-fruF)

3. α-D-fructofuranose (α-D-fruF)

Of these forms, β-D-fruP is generally present in aqueous solution in amajor amount (e.g., about 55% to about 80%), β-D-fruF in a minor amount(e.g., about 15% to about 35%), and α-D-fruF in a nominal amount (e.g.,about 5% to about 10%).

Because β-D-fruP is the predetermined form in solution and because thefuranose forms are reported to be only very slightly sweet(Shallenberger, 1978), it was assumed in the art that the β-D-fruPanomer must be responsible for the perceived sweetness of fructose. Forthis reason, it was assumed that the β-D-fruP anomeric form could beused as an indicator of sweetness, i.e., the more β-D-fruP present, themore sweet the solution should be, and the more β-D-fruF and β-D-fruF atthe expense of the β-D-fruP anomer, the less sweet the solution.

The traditional method of evaluating fructose sweetness is to tastefructose solutions against a sucrose control under like conditions. Froman applications standpoint, this evaluation for "relative sweetness" isthe most practical because if one desires to replace sucrose withfructose in a cold beverage, one needs to know how the sweetness offructose compares with that of sucrose in that beverage system atrefrigerated temperatures. However, from a chemical perspective, itseems cumbersome to correlate fructose anomeric configuration to thesweetness of sucrose. Instead, it was decided to evaluate "absolutesweetness" of fructose, or fructose tasted against a constant fructosestandard which will be referred to herein as "absolute sweetness".

The approach to correlating fructose anomeric distribution as measuredby NMR to fructose "absolute sweetness" was broken down into three keysteps:

(1) First of all, the anomeric distribution of fructose solutions wasmeasured by NMR to confirm the effect of temperature, pH and acidulantsand concentration as reported in the literature.

(2) Then, using this same method, the anomeric distribution of fructosewas determined in actual foods for several reasons:

(a) first of all, to determine if the anomeric distributions of thefructose of foods responded in the same way as the simple solutionsunder the various tested conditions, and

(b) to know the distributions of the fructose in foods and thuseventually attempt to correlate such distributions with sensory testing.

(3) The third step was to actually do sensory testing for "absolutesweetness" of fructose in products with known anomeric distributions.

STEPS 1 AND 2 Anomeric Distribution in Aqueous Solutions

NMR measurements of anomeric distribution of fructose solutions did infact confirm the work by Hyvonen, et al.

FIG. 1 shows the effect of temperature on anomeric distribution offructose solutions (i.e., the percent of each anomer over the range ofabout 5° C. to about 80° C.). The amount of β-D-fruP lessens withincreasing temperature. In other words, the hotter the solution, theless of the β-D-fruP anomer.

FIG. 2 shows the effect of pH. In this case, the effect of acidulant wasthe same for critic and phosphoric acids (i.e., the lines coincide). Theamount of β-D-fruP does not substantially change from pH 3 to 7.

FIG. 3 shows the effect of concentration. Only a very slight increase(probably not significant) can be seen with increasing concentration.

Anomeric Distribution in Food Systems

The anomeric distribution of fructose in food correlated well to that ofthe corresponding aqueous solutions. In other words, distribution of theanomeric forms of fructose in a cherry pie filling, for example, at 29%ds (dry solids) and pH 2.5, matched the aqueous profile at pH 3 and 30%ds. Also, the close correlation between anomeric distribution of simpleaqueous solutions and complex food systems implies that fructoseinteraction with starch in medium and high moisture systems has noeffect on the distribution of fructose anomers.

SUMMARY OF STEPS 1 AND 2

In summary, based on the NMR work with solutions and foods with respectto the effects of temperature, pH, acidulants and concentration, onlytemperature causes a significant anomeric shift between the variousanomers of fructose. From this, it can be concluded that any perceivedchanges in sweetness that are apparently caused by pH or acid type orconcentration cannot be attributed to the mutarotational behavior of thefructose anomers because the anomeric distribution is not dependent uponthese factors.

STEP 3: SENSORY EVALUATION OF "ABSOLUTE SWEETNESS" OF FRUCTOSE INSOLUTION AND FOODS

The third step was to do sensory evaluation of absolute sweetness offructose in solutions and foods.

In the sweetness panelling, the test was designed specifically for"absolute sweetness", not "relative sweetness", of fructose in 10% dssolutions and in cherry pie filling. For aqueous solutions, panelsevaluated solutions at 5° C., 38° C. and 50° C., and at pH 3, 5 and 7with citric, malic and phosphoric acids. For pie fillings (see Example3, below), the effect of temperature at 5° C. and 38° C. was determined(with reference to a control at 25° C.). All samples were tested againsta room temperature fructose standard of unchanging solids. All sampleswere prepared one day prior to panelling and maintained at thetemperature to be tasted to ensure complete mutarotation of the fructoseanomers. Sweetness was calculated by the method described by R. M.Pangborn, "Relative Taste Intensities of Selected Sugars and OrganicAcids", J. Food Science, Vol. 28, p. 725 (1963).

"Absolute sweetness" is to be distinguished from "relative sweetness".In "relative sweetness" evaluations, the sweetness of a test compositionis evaluated versus a sucrose control and thus allows a determination ofthe sweetness of the test composition relative to sucrose. In suchtesting, the compositions are typically water-sweetener solutionscontaining 10% dry solids. The temperature of the solution is adjustedto about 20° C.; and the solution is evaluated by persons trained insensory evaluation. Using such a technique, a sucrose control isarbitrarily defined as 100%. Other sweeteners are then ranked relativeto sucrose.

Fructose usually has a relative sweetness of about 115% as determined bythis particular evaluation technique. Relative sweetness is measured bydetermining the concentration at which a sweetener is judged to besweeter than the control sweetener by one-half of a given taste paneland less sweet than the control by the other half of the test panel. Therelative sweetness is then calculated by dividing the control'sconcentration by the concentration determined for the sweetener beingevaluated. Such techniques are described by R. M. Pangborn, J. FoodScience, Vol. 28, p. 726 (1963).

Results of the sensory work were quite surprising.

In FIG. 4 (and Table A), it can be seen that unlike relative sweetness(see Hyvonen, et al.), absolute sweetness of fructose solutions did notchange with temperature, i.e., fructose solutions at 10% ds tasted assweet at 50% C as at 25° C. and 5° C..

                  TABLE A                                                         ______________________________________                                        Absolute Sweetness of Fructose                                                of Varying Temperatures                                                       Test Sample    Absolute  % of β-D                                        Description    Sweetness*                                                                              Fructofuranose                                       ______________________________________                                         40° F. (5° C.)                                                                98        78.3                                                  77° F. (25° C.)                                                               100       72.3                                                 100° F. (30° C.)                                                               99        69.2                                                 122° F. (50° C.)                                                               96        65.0                                                 ______________________________________                                         *Tested against 10% dry solids aqueous solution of crystalline fructose a     room temperature and a pH of 5.                                          

In the cherry pie fillings, this was also true. Cherry pies which weretasted warm were as sweet as those tasted at refrigerated temperaturesas shown in Table B, below.

                  TABLE B                                                         ______________________________________                                        Effect of Temperature on                                                      Absolute Sweetness of Cherry Pie Filling                                      Formulated With Crystalline Fructose                                          Temperature of  Absolute                                                      Cherry Pie Filling                                                                            Sweetness*                                                                              % β-D-fruP                                     ______________________________________                                         40° F. (5° C.)                                                                 102       80.4                                                 77° F. (25° C.)                                                                100       74.2                                                100° F. (38° C.)                                                                104       69.1                                                ______________________________________                                         *Control  defined at 100 for 25° C.                               

FIG. 5 (and Table C) shows the effect of pH and acidulants. Absolutesweetness is unaffected from pH 5-7 regardless of which acid is present.However, at pH 3, sweetness is depressed; and how much is dependent onwhich acid is used, with citric acid depressing sweetness the most,malic acid next, and phosphoric acid least.

                  TABLE C                                                         ______________________________________                                        Effect of pH on Absolute                                                      Sweetness of Fructose                                                                         Absolute                                                      Test Sample     Sweetness*                                                                              % β-D-fruP                                     ______________________________________                                        pH 3 citric     69        73.6                                                pH 3 malic      78        --                                                  pH 3 phosphoric 90        73.0                                                pH 5            100       72.9                                                pH 7            100       72.7                                                ______________________________________                                         *Tested against a 10% dry solids aqueous solution of crystalline fructose     at room temperatures and a pH of 5.                                      

SUMMARY

In summary, how well does anomeric distribution correlate to fructosesweetness?

FIG. 6 shows that with respect to the effect of temperature, there doesnot appear to be any correlation between the so-called sweet, β-D-fruPanomer and absolute sweetness because it appears that the β-D-fruPdecreases significantly with increasing temperatures while the absolutesweetness of fructose does not change.

FIG. 7 shows that while the amount of β-D-fruP remains constantregardless of pH and the type of acid used, fructose absolute sweetnessis depressed at low pH and with the use of acids. (In this figure,citric acid and phosphoric coincide.)

CONCLUSIONS

Conclusions that were drawn from this study:

(1) It is much more meaningful to consider absolute sweetness offructose rather than relative sweetness when correlating to fructoseanomers.

(2) There is no correlation between absolute sweetness and anomericdistribution of fructose as a function of temperature, pH, and acidused.

(3) Therefore, the use of NMR measurment of fructose anomericdistributions is not useful for the prediction of fructose sweetness.

The above data and conclusions can be used to advantage in formulating avariety of materials which are intended for consumption, or at leastcontact with the mouth of the user, such materials being hereingenerically designated as edible materials. Typical illustrativeexamples of edible materials which may be sweetened according to thisinvention are fruits, vegetables, juices or other liquid preparationsmade from fruits or vegetables, meat products, particularly thoseconventionally treated with sweetened liquors, such as bacon, and ham,milk products (such as chocolate dairy drinks), egg products(such aseggnogs and custards), angel food mixes, salad dressings, pickles andrelishes, ice creams, sherbets and ices, ice milk products, bakeryproducts, icings, confections and confection toppings, syrups andflavors, cake and pastry mixes, beverages, such as carbonated softdrinks, fruit "ades" (e.g., lemonade), wines, dietary-type foods, coughsyrups and other medicinal preparations, such as toothpastes, powders,foams and denture-retaining adhesives, mouth washes and similar oralantiseptic liquids, tobacco products, adhesives for gumming stamps,envelopes, labels and the like.

Foodstuffs which are particularly appropriate in the context of thisinvention include those which are commonly consumed both hot and cold.Examples include processed meats, fish, or fowl (e.g., wieners, luncheonmeats, sausages, hams, surimi, etc.); pork and beans; sauces, coatings,and breadings (e.g., salad dressings, barbecue sauces, chocolate sauces,coating mixtures of fried chicken, etc.); infused fruit and fruitfillings; instant oatmeal; table syrup; meat or pastry glazes (e.g., hamglaze or cake frostings); beverages (e.g., flavored coffee mixes,instant tea mixes, coffee whiteners, baby formula, milk shakes, mealreplacement beverage mixes); sweetened condensed milk; soups; cheesefoods; cheese spreads; and breads (e.g., sweet rolls or fruit breads).

Further, while the above data and conclusions are most advantageouslyemployed when crystalline fructose is the sole sweetener used in a givenformulation, the data may be advantageously employed in the use of ablend of sweetening agents, said blend being comprised of fructose.Examples of other sweetening agents include nutritive saccharidesweeteners, e.g., dextrose, sucrose, corn syrup, high fructose cornsyrup, semi-crystalline fructose, and the like, as well as highintensity sweeteners, e.g., dipeptides such as aspartame andproteinaceous materials such as thaumatin. Further examples include highintensity sweeteners, e.g., saccharin, acesulfame-K, and chlorodeoxy,sugars, and glycyrrhizin. In general, however, the sweetening agentemployed herein should derive a predominant portion of its sweeteningeffect from fructose, e.g., greater than 90% by weight of saccharidesweetener solids should be fructose.

In using a sweetening agent comprised of fructose in accordance withthese teachings, it can be incorporated in the material to be sweetenedin the amount required to attain the desired level of sweetness.Moreover, the technique of sweetening materials in accordance with theseteachings offers no difficulty because the sweetening agent, as a mix oras separate components, can be simply incorporated with the material tobe sweetened. The sweetening agent may be added directly to the materialor it may be first incorporated with a diluent to increase their bulkand added to the material. As diluent, if needed, one may use liquid orsolid carriers, such as water, starch, maltodextrin, corn syrup, cornsyrup solids, sorbitol, salt, or other non-toxic substances compatiblewith the material to be sweetened. In fact, an aqueous solution ofcrystalline fructose, e.g., at 70% to 80% dry solids, may be anadvantageous form of liquid fructose for use in accordance with theseteachings. Advantages, methods of preparation, and other usefulinformation relating to such a concept as disclosed in U.S. Ser. No.173,404, filed Mar. 25, 1988, the disclosure of which is incorporatedherein by reference.

A foodstuff mix formulation useful in this invention will generallycontain a flavoring agent in addition to the sweetener. The use ofvarious flavors is within the skill of the formulation art. Variousflavors and spices are discussed and referenced in J. A. Rogers and F.Fischetti, "Flavors and Spices", Encyclopedia of Chemical Technology,Vol. 10, pp. 456-488 (Kirk-Othmer eds., John Wiley & Sons, 3d ed. 1980),the disclosure of which is incorporated by reference.

A detailed description of the aspects of this invention relating totemperature and acidulant phenomena will follow. While the broadestsense of the term "dry foodstuff mix" will encompass many differenttypes of edible materials, preferred embodiments of this aspect of thisinvention relate to dry mixes useful in preparing "instant" beverages,i.e., beverages prepared from a dry mix by mixing with an edible liquidwithout cooking (especially fruit-flavored dry mixes, e.g., Kool-Aid™brand from General Foods). Such dry mixes also typically contain aflavoring concentrate and/or a coloring agent. Examples of typicalflavor concentrates include natural or imitation fruit flavors (e.g.,dried fruit powders) and/or plant products, for example, cocoa (e.g.,alkali process instant cocoa), and dried extracts such as instant teaand instant coffee. Coloring agents and other examples of flavoringagents are well known in the beverage art.

In the cooling and/or heating steps of the methods of this invention,the means of cooling and/or heating are not critical, so long as theyare effective to cool and/or heat and result in an edible product thatis organoleptically acceptable. In order to heat or cool a mixture, itis contemplated that one or more components can be heated or cooledprior to mixing to yield a mixture that is relatively hot or cold, asdesired. For example, to make a hot cocoa beverage, it is common to heatthe milk and then add a room temperature dry cocoa mix. Likewise, coldchocolate milk is usually prepared by stirring a room temperature dryinstant cocoa mix into cold milk.

Particularly preferred embodiments of this invention employ a drybeverage mix which contains a flavoring agent selected from the groupconsisting of a natural fruit flavor (e.g., fruit powders), an imitationfruit flavor, cocoa (e.g., an "instant" form thereof), a tea extract, acoffee extract, and mixtures of two or more of the foregoing. Ingeneral, such a dry mix will be comprised of a major amount by weight ofsweetener (e.g., consisting of crystalline fructose) and a minor amountby weight of such a flavoring agent. Beverages made in accordance withthe teachings herein will generally be comprised of a major amount byweight of an edible liquid (e.g., at least 85% by weight water), andminor amounts by weight of solids, the predominant solids beingsweetener solids, e.g., from about 5% to 15% by weight of the beverage.

With respect to the serving temperatures of the invention, differentfoods are commonly served within different ranges of temperature, therange generally being a matter of custom and/or personal preference.Because of variations in the efficiencies of heating and/or cooling,these ranges and the temperatures of individual servings within theseranges can vary widely, with or without the intent or knowledge of theserver and/or consumer. However, a cold beverage, for example, willgenerally have a desired maximum serving temperature, i.e., atemperature above which a substantial segment of a potential consumingpublic will consider the beverage unacceptable. Thus, the temperature ofa given serving of a cold beverage at the time of consumption can varywidely, but will generally be below a maximum serving temperaturedesired by the consumer. It is an advantage of this invention that whilethe temperature may very widely within a range, the sweetness perceivedby a consumer should not vary. Thus, a product having consistentsweetness over temperature can be formulated, manufactured, sold andconsumed.

The use of acidulants, particularly in beverages, is well known in theart. See, for example, J. Woodroof and G. Phillips, Beverages:Carbonated and Non-Carbonated, (3d ed. AVI Publ. Co. 1981), thepertinent portions (pertinent with respect to all aspects of thisinvention) of which are incorporated by reference. Given the generalteachings herein, one of ordinary skill in the art of formulatingvarious foods should be able to modify a given formulation in accordancewith this invention to optimize the properties desired therein. In thisrespect, while certain embodiments of this invention are limited inscope to the use of a plurality of acidulants, it is contemplated thatthe teachings herein will be useful in the context of total substitutionof a particular acid with another acid, e.g., total replacement ofcitric with malic or phosphoric.

A discussion of general principles relating particularly to dry mixbeverage formulation is appropriate. If a commercially availablebeverage flavor base is used for the preparation of the dry beverage mixof the present invention, various substances may optionally be added tothe flavor base in processing it in accordance with the presenceinvention to provide a dry beverage mix. The only criterion that limitsthe possible inclusion of any optional ingredient is that it must beacceptable for use in an edible food product. Other than thisrestriction, only the appearance of an undesirable off-taste oroff-color for a particular beverage will place a practical limitation onthe addition of any desired material. As those skilled in the art willappreciate, the variety of different materials which may be added isextremely broad indeed. For example, certain embodiments of the presentinvention are concerned with a dry beverage mix which will be dissolvedin water at the point of consumption. In doing this, a consumer willmost likely use tap water which is slightly alkaline due to the mineralsalts dissolved therein. Thus, to neutralize this additional alkalinity,additional acid may be needed to achieve the same intensity ofacidulation as that achieved when distilled or de-ionized water is usedas a beverage base.

Other materials which may be included in the mix are various additionalflavoring ingredients which may be added to the commercial flavor baseto modify its flavor, accentuate any especially preferred flavor notes,or replace any flavor notes which may be volatilized and lost duringprocessing into a dry mix. Some of the more common flavoring ingredientswhich can be added to a cola beverage include, for example, extract ofcoca leaves, neroli oil, lime oil, lemon oil, orange oil, nutmeg oil,vanilla extract or cassia oil. Other flavoring materials for colas orany other desired beverage may be found in published formulation recipesfor the particular beverage flavor desired.

Other types of materials, such as food colorings, for example, U.S.Certified Food Colors or caramel coloring; stimulants, for example,caffeine; artificial sweeteners, for example, saccharine; bodyingagents, for example, maltodextrin or sodium carboxymethylcellulose;forming agents, for example, licorice root extract or saponin-bearingextract of soaproot; or preservatives, for example, sodium benzoate,propylene glycol or ascorbic acid may advantageously be added to theflavor base to achieve the respective desired results. Stabilizers forcola, e.g., monosodium phosphate, may also be added to the flavor base.

The ingredients of the dry mix can be a simple blend, which is notnecessarily homogeneous in any sense. However, the method disclosed inU.S. Pat. No. 4,199,610 (Hughes, et al.) may, nonetheless, be useful. Inthat method, a uniform slurry of pulverized sugar (e.g., fructose),liquid flavor and phosphoric acid is vacuum dried to prepare a drybeverage mix.

In forming the dry beverage mix of Hughes, et al., the proper flavorbase is blended with finely powdered sugar to form a thick, homogeneousslurry. In this regard, it may be necessary to add a small amount ofwater for workability and to achieve thorough admixing of theingredients. Only so much water as is necessary for these purposesshould be added since any added water is subsequently removed during thedrying operation and excess water only contributes to the inefficiencyof the process. Any type of conventional mixing means may be used forthis purpose, as long as a thorough mixing is achieved. Typically,however, the temperature of the slurry is kept below about 100° F.during admixture to avoid any loss of volatiles or heat degradation offlavor components. With this consideration in mind, it was thusrecommended that low-shear mixing means be employed, since these willimpart less energy to the mixture, and correspondingly, less heat.

The admixture of flavor base, the powdered beverage sugar, and anyoptional ingredients is then dried to a substantial dryness usingconventional vacuum or freeze drying techniques to produce a drybeverage mix. Substantial dryness is that state where the matter has theappearance of a free-flowing, dry-to-the-touch solid. This willtypically mean drying to a final moisture content of less than about 1%,and preferably, less than about 0.5%. That the slurry is dried by vacuumdrying, or equivalent techniques, causes the drying material to foam, soas to form a beverage mix which is rapidly dissolvable in waterrequiring only a minimum amount of agitation. Vacuum drying techniquesare known to those skilled in the art and will not be detailed hereinfor purposes of brevity. Best results may be obtained if the slurry isdried within a period of about twenty-four hours and the temperature ofthe slurry is not raised above about 100° F., and preferably above 50°F., during the drying process. Conventional freeze drying techniques areequivalent to the vacuum drying techniques in the results obtained andmay thus be advantageously employed. Freeze drying basically involvesfreezing to temperatures of about -10° F. to about -40° F. and removingthe water by sublimation as the frozen slurry is gradually warmed undervacuum conditions. Again, any of the conventional freeze-dryingtechniques known to those skilled in the art are suitable.

The dried product resulting from the dehydration step is ground byconventional size reduction techniques so as to make it more readilydissolvable when added to water and to enhance the appearance of thefinal product. Depending upon the fineness to which the particles areground, they may be screened to obtain groups of approximately uniformparticle size.

The dry beverage mixes can be packaged in suitable aliquot portions forsubsequent dissolution in a predetermined amount of water to obtainflavorful beverage ready for consumption. The dry beverage mixes of thepresent invention may be advantageously employed with a variety ofcarbonation systems to provide suitably carbonated, flavorful beverages.For instance, the dry beverage mixes as disclosed herein can be added topre-carbonated water, or, the dry beverage particles can be combinedwith an economical point-of-consumption carbonation system and thiscombination then added to tap water to provide a convenient, carbonatedbeverage. Examples of suitable sources of pre-carbonated water are theuse of bottled pre-carbonated water, commonly known as "club soda" orthe use of pressure carbonators which utilize CO₂ -charged cylinders tocarbonate water as it is dispensed, such as is done at a soda fountain.Examples of point-of-consumption systems which utilize regular tap waterfor the beverage include the use of a "chemical couple" such as thosedisclosed in Mitchell, et al., U.S. Pat. No. 3,241,977, issued Mar. 22,1966, or Hovey, U.S. Pat. No. 3,492,671, issued Jan. 27, 1970; or theuse of CO₂ -loaded zeolite molecular sieves, such as that disclosed inU.S. Pat. No. 3,966,994, issued June 6, 1976. The latter-namedcarbonation system, i.e., the use of CO₂ -loaded zeolite molecularsieves, is especially preferred in the practice of the presentinvention.

It is important that the dry mixes of the present invention be packagedin a moisture-proof container, in that the particles are hygroscopic innature and that the particle physical structure collapses when wetted.Also, exposure to moisture would activate any phosphoric acid present inthe dry mix which would lead to degradiation of the sugar and flavorcomponents in the mix. A convenient method for insuring that these mixesare not degraded by exposure to moisture during storage periods is tohave them packaged in the presence of a desiccant. The CO₂ -loadedmolecular sieves disclosed in the above-mentioned U.S. Pat. No.3,966,994 is a suitable desiccant for such purposes. Thus, the presenceof such CO₂ -loaded zeolite molecular sieves in combination with the dryflavor mix has multiple advantages in that they provide protection ofthe dry mixes during storage, provide a convenient and sufficientcarbonation system during use, and the effervescent action resultingform the molecular sieves immersed in water is sufficient to provideadequate agitation for the dissolution of the dry mixes.

EXAMPLES EXAMPLE 1

Instant Fruit Drink from Dry Mix Concentrate

An instant fruit drink (cherry flavored) is made from a dry mixconsisting of:

    ______________________________________                                        Ingredient              Parts by Weight                                       ______________________________________                                        Crystalline Fructose    83                                                    (KRYSTAR ™ brand,                                                          A. E. Staley Manufacturing Co.)                                               Citric Acid             1.8                                                   Ascorbic Acid           0.1                                                   Tricalcium Phosphate    0.015                                                 Maltodextrin (5 D.E.)   2.3                                                   Color (Warner Jenkinson Color No. 7425)                                                               0.035                                                 Cherry Flavor (Universal Flavors)                                                                     0.285                                                                         87.535                                                ______________________________________                                    

To prepare the dry mix, dry blend the foregoing ingredients. To preparea beverage, mix the 87.535 parts of the dry blend with 912.465 parts byweight water which should yield 1,000 parts by weight cherry drink mix.Divide the 1,000 parts into three individual servings and cool all toapproximately the same temperature of 5° C.. Consume one servingmaintained at 5° C. until consumption, allow a second to warm to about25° C. prior to consuming, and heat one to about 38° C. prior toconsuming.

Example 2 Instant Vanilla Pudding From Dry Mix

An instant vanilla pudding can be prepared from the followingingredients:

    ______________________________________                                                               Parts by Weight                                        Ingredient             (grams)                                                ______________________________________                                        Crystalline Fructose (see Ex. 1)                                                                     74.0                                                   Emulsifier (Durem ™ 114, Durkee Foods)                                                            0.5                                                    Vegetable Oil          0.5                                                    Disodium Phosphate     0.6                                                    Tetrasodium Phosphate  1.0                                                    Table Salt             0.5                                                    Color (Warner Jenkinson No. 8038,                                                                    0.4                                                    egg shade - wt. of total liquid)                                              Imitation Vanilla Flavor                                                                             3.0                                                    (wt. of total liquid)                                                         Starch (STARCO ™ 447, A. E. Staley                                                                17.5                                                   Mfg. Co.)                                                                     Total                  98.0                                                   ______________________________________                                    

A dry mix instant pudding composition is prepared as follows: Melt theemulsifier and vegetable oil together and then coat melted blend ontothe crystalline fructose while mixing with a conventional householdmixer at low speed. Add the remaining dry ingredients and mix into theoil-sweetener mixture to form a dry milk.

An instant pudding can be prepared from the dry mix as follows: Make upat least three individual packets of 98 grams each and store. Add one 98g packet of dry mix to 450 ml of cold (5° C.) milk and mix for twominutes with conventional household mixer at low speed. Add a second 98g packet of the dry mix to 450 ml of milk at room temperature (25° C.)and mix as above. Add a third 98 g packet of the dry mix to 450 ml ofwarm milk (38° C.) and mix as above.

Example 3

Several cook-up cherry pies were baked to evaluate fructose (KRYSTAR™)in the system by NMR and for sensory evaluation. All sweeteners intypical formula were replaced with KRYSTAR™ brand crystalline fructose.

    ______________________________________                                                       Total   Solids                                                                Wt.     %       g                                              ______________________________________                                        Part A                                                                        Frozen Cherries  200.00    15.1    30.2                                       KRYSTAR 300      356.00    100     356.0                                      Salt             2.00      100     2.0                                        Citric Acid      2.00      100     2.0                                        Water            404.00                                                       Part B                                                                        Water            160.00                                                       Starch (REZISTA ™ F1600E                                                                    76.00     88      66.88                                      available from A. E. Staley                                                   Mfg. Co.)                                                                     Part C                                                                        Frozen Cherries  800.00    15.1    120.8                                                       2000.00           577.88                                     ______________________________________                                    

The resulting filling is 28.89% solids (577.88/2000.00) and 17.8%sweetener solids (356.0/577.88).

Procedure:

1. Part A was placed in a steam kettle and brought to a boil.

2. Part B was added and the mixture was cooked until clear, then cooked90 seconds longer, after which the steam was turned off.

3. Part C was added and the mixture was agitated until cool.

4. 800.0 g was placed in a pie shell, sealed and baked at 425° F. for 45minutes

Example 4

A control cherry drink dry mix can be prepared by thoroughly dryblending the following:

    ______________________________________                                        Ingredient            Wt. (grams)                                             ______________________________________                                        KRYSTAR ™ Crystalline Fructose                                                                   82.52                                                   Citric Acid           1.7928                                                  Cherry Flavor N/A, #S-3447                                                                          0.278                                                   (Warner Jenkinson)                                                            FD & C Red #40; 7700  0.0348                                                  (Warner Jenkinson)                                                            Ascorbic Acid)        0.0957                                                  Tricalcium Phosphate  0.0174                                                  Maltodextrin (5 D.E.) 2.289                                                                         87.03 g                                                 ______________________________________                                    

A control cherry drink beverage can be prepared by pouring the 87.03grams of the above dry mix into a one liter container and adding waterto the one liter line. The resulting one liter of beverage will contain1.7928 g of citric acid and should have a pH of about 3 (e.g., 2.7-3.0,depending on the acidity/alkalinity of the water used).

The following table, Table D, shows the adjustment of citric acidcontent of the beverage (obtained by using phosphoric acid (Phos.,below) alone or both citric acid and phosphoric acid in the dry mix inthe amount shown) to replace the indicated percentage acidity and thewt. % reduction of the amount of crystalline fructose that one shouldmake to obtain a beverage of equal sweetness.

                  TABLE D                                                         ______________________________________                                        Replacement With Phos. (75%) @ 0, 10, 25, 50, 75, 100%                                                  Wt. %                                                           Acid          reduction in                                                    (grams in 1 liter                                                                           KRYSTAR to                                          % Acidity from                                                                            finished product)                                                                           obtain equivalent                                   Phos./Citric                                                                              Phos.    Citric   sweetness                                       ______________________________________                                         0/100      0.0000   1.7928   0                                               10/90       0.0128   1.6135   2.95                                            25/75       0.0319   1.3446   7.07                                            50/50       0.0638   0.8964   13.21                                           75/25       0.0957   0.4482   18.58                                           100/0       0.1276   0        23.31                                           ______________________________________                                    

Likewise, malic acid can be substituted for citric acid as shown inTable E, below.

                  TABLE E                                                         ______________________________________                                        Replacement With Malic @ 0, 10, 25, 50, 75, 100%                                                        Wt. %                                                           Acid          reduction in                                                    (grams in 1 liter                                                                           KRYSTAR to                                          % Acidity from                                                                            finished product)                                                                           obtain equivalent                                   Malic/Citric                                                                              Malic    Citric   sweetness                                       ______________________________________                                         0/100      0        1.7928   0                                               10/90       0.2502   1.6135   1.28                                            25/75       0.6255   1.3446   3.16                                            50/50       1.2510   0.8964   6.12                                            75/25       1.8764   0.4482   8.91                                            100/0       2.5019   0        11.54                                           ______________________________________                                    

While the above examples serve to illustrate and/or clarify certainaspects of this invention, variations thereof in accordance with thespirit of the teachings herein should be considered within the scope ofthis invention. All parts, percentages, and ratios stated herein are byweight, unless noted otherwise.

What is claimed is:
 1. A method of preparing a foodstuff for consumptioncomprising:(a) mixing a dry foodstuff mix, said foodstuff mix comprisinga particulate solid consisting of crystalline fructose, with an edibleliquid to form a mixture; (b) cooling a member selected from the groupconsisting of said mixture and one or more components thereof, to reducethe temperature of said mixture to a first temperature within a range ofdesired maximum serving temperatures for said mixture; (c) providing forthe temperature of said mixture to rise to a second temperature withinsaid range of desired maximum serving temperatures; and (d) serving saidmixture for consumption as a foodstuff at said second temperature.
 2. Amethod of alternately preparing hot and cold foodstuffs for consumptioncomprising:(a) mixing a first portion of a bulk reserve of a dryfoodstuff mix, said dry foodstuff mix comprising a particulate solidconsisting of crystalline fructose, with an edible liquid to form afirst mixture; (b) heating a member selected from the group consistingof said first mixture and one or more components thereof, to elevate thetemperature of said first mixture to a temperature suitable for servingsaid first mixture for consumption; (c) mixing a second portion of saidbulk reserve of said dry foodstuff mix with an edible liquid to form asecond mixture; and (d) cooling a member selected from the groupconsisting of said second mixture and one or more components thereof, toreduce the temperature of said mixture to a temperature suitable forserving said first mixture for consumption.
 3. A method of formulating asweetened and acidulated foodstuff comprising:(a) substituting at leasta portion of the sweetener in a given sweetened foodstuff formulationwith a particulate solid consisting of crystalline fructose, saidfoodstuff having a pH of below about 5 when consumed; and (b) employinga plurality of acidulants to adjust the sweetness of said formulation,said plurality comprising citric acid, or a salt thereof, and an edible,non-citric, fructo-sweetness active acid, or a salt thereof.
 4. Abeverage concentrate comprising:(a) a particulate solid consisting ofcrystalline of fructose, said fructose being present in a first amount;and (b) an acidulant comprised of citric acid in a second amount, and anedible, non-citric, fructo-sweetness active acid in a third amount;(i)said second and third amounts are, in the aggregate, sufficient toprovide a beverage having a pH of less than about 5; (ii) said firstamount is sufficient, in relation to said second and third amounts, toprovide a sweetened beverage.
 5. A beverage concentrate of claim 4wherein said sweetener consists of crystalline fructose in a majoramount by weight of said concentrate and said acidulant is comprised ofa major amount by weight of said acidulant of citric acid and a minoramount by weight of an acid selected from the group consisting of (1)malic acid, (2) edible derivatives of malic acid, (3) phosphoric acid,(4) edible derivatives of phosphoric acid, and (5) mixtures selectedfrom one or more of (1), (2), (3) and (4).